JPS6044556A - Water-insoluble monoazo compound and dyeing using it - Google Patents

Abstract

NEW MATERIAL:A compound shown by the formula I [R is 1-4C alkyl; X is H, or bromo; K is formula II-formula V (R1 is H, chloro, methyl, acetylamino, etc.; R2 is H, chloro, methyl, methoxy, etc.; R3 and R4 are H, 1-4C alkyl, aryl, benzyl, cycanoethyl, etc., and R3 and R4 are not H at the same time; R5 is chloro, methyl, or ethyl; R6 is H, methyl, or phenyl; R7 is methyl, or 2-5C alkoxycarbonyl; R8 is H, 1-4C alkyl, etc.)]. EXAMPLE:A compound shown by the fomrula VI. USE:Dyeing and printing hydrophobic fiber, especially polyester, triacetate fiber, etc. in purple, red, or yellow with improved fastness, light resistance, etc. PREPARATION:An aniline derivative shown by the formula VI (e.g., 2,6-dicyano- 3-methyl-5-methoxycarbonylmethyl-aniline, etc.) is diazotized, and coupled with a coupling component shown by the formula KH.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an unnatural monoazo compound and a method for dyeing hydrophobic fibers using the same.

More specifically, formula (I) [In formula (I), I(, represents an alkyl group having 1 to 4 carbon atoms, X represents hydrogen or bromine, and 1 represents formula (II), (
III) GV) or ■■also 8 (Formula (II), (III), (IV) and (
V) iC oitellq is hydrogen, chloro, methyl group, methoxy group, ethoxy group, acetylamino group, propionylamino group, benzoylamino group, methylsulfonylamino group or ethylsulfonylamino group;
chloro, methyl group, methoxy group or ethoxy group, R3
, R4 is hydrogen, an alkyl group having 1 to 4 carbon atoms, an allyl group,
benzyl group, cyanethyl group, alkoxyalkyl group having 3 to 4 carbon atoms, hydroxyalkyl group having 2 to 4 carbon atoms,
Acyloxyalkyl group having 4 to 6 carbon atoms, 3 to 7 carbon atoms
an alkoxycarbonylalkyl group or an alkoxycarbonyloxyalkyl group having 4 to 7 carbon atoms (however, R3,
R4 is not both hydrogen), R5 is chloro, methyl group or ethyl group, R6 is hydrogen, methyl group or phenyl group, R7 is methyl group or alkoxycarbonyl having 2 to 5 carbon atoms M't N The present invention relates to an insoluble monoazo compound represented by "8 represents hydrogen, an alkyl group having 1 to 4 carbon atoms, or an alkoxyalkyl group having 4 to 7 carbon atoms, respectively" and a method for dyeing hydrophobic fibers using the same.

The monoazo compound of formula (I) according to the present invention is a monoazo compound of formula (VD(
In formula (Vl), rt and x have the same meanings as above)
The aniline derivative represented by is diazotized to produce ■gl-1 (
1 (represents the same meaning as above).

Specific examples of the aniline derivatives represented by the formula (VI) used in the present invention include 2,6-dicyano-3-methyl-5-methoxycarbonyl, 2,6-dicyano-3-methyl-5-methoxycarbonyl, 2,6-dicyano- 3-Methyl-5-ethoxycarbonylmethyl-aniline, 2,6-dicyano-3-methyl-5-butoxycarbonylmethyl-aniline, 2,6
Examples include -dicyano-3-methyl-4-bromo-5-methoxycarbonylmethyl-aniline, 2,6-dicyano-3-methyl-4-bromo-5-inglobyloxycarbonylmethyl-aniline, etc. This is a novel intermediate, which is produced by condensing and ring-closing acetoacetic acid lower alkyl ester in alcohol in the presence of sodium alcoholade, and then acting on this condensate as a bromine compound to form the 4-bromo-
It is used to produce derivatives.

Campling component formula (III) used in the present invention
~M is a camping component commonly used when manufacturing azo disperse dyes, but to give some specific examples, N-
Ethyl-N-cyanoethyl-aniline, N-methyl-N
-acetoxyethyl-meta-toluidine N,N--SH-y-/l/-7cetylmethamine, N,N-diallyl-2-methoxy-5-acetylamino-aniline,
N,N-diethyl-3-ethylsulfonylamino-aniline, N,N-c(β-hydroxyethyl)-3-
Benzoylamino-aniline, N,N-di(methoxycarbonylethyl)-3-acetylamino-aniline,
Ortho-cresol 3-chloro-phenol 1-phenyl-3-methyl-pyrasolone, 1-phenyl-3-
Methoxyluponyl-hyrasolone, 1-(3:4'-dichloro-phenyl)-3-methyl-hyrasolone, 1-butyl-3-cyano-4-methyl-6-hydroxypyritone (-2), Diazotization and coupling in the present invention can be carried out by conventional methods. I can do it. For example, when the aniline derivative of formula (1) is treated with nitrosyl sulfuric acid in a mixed solution of sulfuric acid or acetic acid propionic acid at 5°C or less, it is easily diazotized, and this diazotized solution is converted into an aqueous solution containing a coupling component or an aqueous solution containing a coupling component. When added to the dispersion at 10°C or lower, the coupling reaction easily proceeds. At this time, it is preferable to adjust the PL by adding soda ash, sodium acetate, etc. as necessary.

The monoazo compound obtained according to the present invention is suitable for dyeing or printing various hydrophobic fibers, particularly polyester fibers, triacetate fibers, etc.

In dyeing, the azo compound is dispersed with a dispersant and, if necessary, mixed with other dyeing aids to form a dye composition. That is, the monoazo compound may be an anionic dispersant such as a formaldehyde condensate of naphthalene sulfonic acid, lignin sulfonic acid, or sulfated creosote oil, or a nonionic dispersant such as a block copolymer of ethylene oxide and propylene oxide, or an ethylene oxide adduct of alkylphenol. A dye composition can be obtained by thorough wet milling using a ball mill, xantho mill, etc. in the presence of an activator and a small amount of water. Using this composition, conventional high-temperature dyeing, carrier dyeing, thermosol dyeing, textile printing, etc. are carried out. In the case of continuous dyeing, use anti-migration agents such as sodium alginate and anti-reduction agents, and in the case of textile printing,
It is preferable to use natural thickeners, synthetic thickeners, pH adjusters, deep dyes, etc. in combination.

In addition, by overprinting a discharge printing paste containing a reducing agent and an alkaline agent, pattern printing such as anti-discharge printing and color discharge printing can be performed.

The monoazo compound according to the present invention can be used to dye various colors such as purple, red, and yellow, but these hues are extremely vivid, and the dyed products have excellent light fastness and are resistant to moisture, heat treatment, etc. Has excellent fastness. In addition, since this compound has a carboxylic acid ester group in its structure, the undyed monoazo compound has the property of being easily removed by alkali, has little staining, and is difficult to remove in alkali discharge printing. It also exhibits extremely excellent discharge printing properties.

The present invention will be specifically explained below with reference to examples, in which "parts" and "%" refer to "parts by weight" and "% by weight," respectively.
” is shown.

Example 1 2.6- to 50 parts of acetic acid-propionic acid (4:1) mixture
Add 57 parts of dicyano-3-methyl-5-methoxycarbonylmethyl-aniline, stir, and dropwise add 6.7 parts of 44% nitrosyl sulfuric acid at 3°C or lower. 0 part 3℃
After stirring for 30 minutes, diazotization is complete. 6.4 parts of N,N-diethyl-3-ethylsulfonylamino-aniline is dissolved in 300 parts of 2% hydrochloric acid, and the diazotized solution is added dropwise while stirring at 10°C or lower. Add 500 parts of ice water to precipitate crystals, separate in a furnace, wash with water and dry.

85 parts of a monoazo compound having the following structure was obtained, and this compound dyes polyester fibers in a bright red color.

λ+nax 524 nm (85% acetone aqueous solution)
2,6-dicyano-3-methyl-5 used in this example
-Methoxycarbonylmethyl-aniline is synthesized as follows.

To 50 parts of methanol are added 23.2 parts of methyl acetoacetate, 13.2 parts of malonitrile, and 3.6 parts of a 28% methanol solution of sodium methylate, and the mixture is refluxed for 2 hours. Once cooled to room temperature, 19 parts of a 28% methanol solution of sodium methylate was added, and after stirring for 1 hour at 10 to 20°C,
The mixture was heated to 60°C for 15 minutes and stirred at 60-65°C for 15 minutes.

After cooling, the mixture was poured into 600 parts of ice water with stirring, and 20 parts of common salt was added to precipitate crystals. If you wash and dry it separately, it will be 2,6-
12.5 parts of dicyano-3-methyl-5=methoxycarbonylmethyl-aniline are obtained. Recrystallization from alcohol showed no Inp of 136-138°C.

Example 2 7.3 parts of 2,6-dicyano-3-methyl-5-ethoxycarbonylmethyl-aniline was added to 50 parts of acetic acid-propionic acid (4:1), and 44% nitrosyl Add 9 parts of sulfuric acid dropwise. After stirring for 30 minutes, diazotization ends. N,N-di(methoxycarbonylethyl)-
The diazotized solution is added dropwise to 300 parts of a 2% hydrochloric acid solution containing 9.7 parts of 3-acetylamino-aniline at 10°C or below. Add 500 parts of ice water, stir for 1 hour, separate the precipitated crystals, wash with water and dry.

13 parts of a monoazo compound having the following structure are obtained.

λmax 518 parts m (85% acetone aqueous solution) Dyeing hue of polyester fiber 2,6-dicyano-3-methyl-5 used in the red book example
-Ethoxycarbonylmethyl-aniline is similarly synthesized using ethyl acetoacetate instead of methyl acetoacetate as described in Example 1. mp135-
137°G Example 3 6.5 parts of 2,6-dicyano-3-methyl-4-bromo-5-ethoxycarbonylmethyl-aniline was added to 50 parts of acetic acid-propionic acid (4:1), and the mixture was heated at 3°C with stirring. 4 below
Add 6 parts of 4% nitrosyl sulfate dropwise. After stirring for 30 minutes, diazotization is completed. N.

N-di(methoxycarbonylethyl)-3-methyl-
The diazotization solution is added dropwise to 300 parts of a 2% hydrochloric acid solution containing 5.6 parts of Ayurif at 10°C or lower. ice water 500
After stirring for 1 hour, the precipitated crystals were separated, washed with water, and dried. 9 parts of a monoazo compound having the following structure are obtained.

λmax 506 parts m (85% acetone aqueous solution) Dyeing hue of polyester fiber 2,6-dicyano-3-methyl-4 used in the red book example
-Bromo-5-ethoxycarbonylmethyl-aniline is synthesized as follows.

2,6-dicyano-3-methyl-5 as described in Example 2
7.4 parts of -ethoxycarbonylmethyl-aniline are stirred with 6.6 parts of anhydrous sodium acetate in 60 parts of acetic acid. A solution of 6 parts of bromine dissolved in 10 parts of acetic acid is added dropwise at room temperature over a period of about 2 hours. After stirring for another 2 hours at 2°C, the mixture was poured into 250 parts of ice water. The precipitated crystals are separated, washed with water and dried to obtain 8 parts of 2,6-cycyano-3-methyl-5-ethoxycarbonylmethyl-4-bromo-aniline. When recrystallized from alcohol, Inp 1 jO−
It shows 152°C.

Example 4 To 50 parts of acetic acid-propionic acid (4:1) are added 5.4 parts of 2,6-dicyano-3-methyl-5-butoxyfluoro/l/methyl-aniline. 44% under stirring at 3℃ or less
When 6 parts of nitrosyl sulfuric acid is added dropwise and stirred for 30 minutes, diazotization is completed. ■-Butyl-3-cyano-4-methyl-
4.6 parts of 6-hydroxyviridone (-2) and 400 parts of water
1 part and 4 parts of soda ash, and the diazotized liquid was gradually added dropwise at 10° C. or lower. During this time, do not add 10% soda ash solution and adjust pI-1 to 7-8. The precipitated crystals are separated from each other, washed with water, and dried. 9.4 parts of a monoazo compound having the following structure are obtained.

λ+nax 418 Nephew (85% acetone aqueous solution) Dyed hue of polyester fiber Yellow 2,6-dicyano-3-methyl-5 used in this example
-Butoxycarbonylmethyl-aniline is synthesized by using butyl acetoacetate instead of methyl acetoacetate as described in Example 1 and performing the same procedure. mp160
-164°C Examples 5 to 44° In the same manner as in Examples 1 to 4, the aniline derivative of formula (Vl) is diazotized and camped to the coupling component of K I-I, resulting in a monoazo compound of formula (I). can get.

(IV) (El Example 45゜30 parts of monoamine compound obtained in Example 1 Demol N
Add a small amount of water to 40 parts of anionic dispersant (anionic dispersant, manufactured by Kako Atlas) and 30 parts of Demol C (anionic dispersant, manufactured by Kako Atlas) to make a slurry, thoroughly wet-pulverize with a sand mill to make a finely dispersed state, and spray. Dry with a hair dryer. A dye composition is obtained which is well dispersed in water. 3,000 parts of water are added to 4 parts of this dye composition to form a dispersion, and a small amount of acetic acid is added to adjust pi-1 to 5. 100 parts of a polyester textured yarn fabric is immersed and dyed under pressure at 130° C. and at room temperature for 1 hour. The dyed fabric is then thoroughly soaped and dried to obtain a bright red dyed product. This product has good sunlight, sublimation and wet fastness.

Example 46 1000 parts of water is added to 20 parts of the dye composition described in Example 45 to prepare a dispersion. Dip the polyester processed yarn fabric,
Next, it is squeezed at a weight increase of 70% by 1, dried once at 100°C, and then subjected to a dry heat treatment at 210°C for 60 seconds. Further, perform reduction washing and wash thoroughly with water. A uniformly red dyed cloth is obtained.

Example 47 Dye composition based on the monoazo compound described in Example 4 4
Department fI? '60 parts Liquor Tartaric acid 0.2 parts Sodium chlorite 05 parts Water 35.5 parts Total 100 parts × Original paste A mixture having the above composition is mixed in a homomixer to prepare a printing paste. Stamp the polyester fiber fabric with this printing paste, and
0 part Dry for 30 minutes at 5°C.

Next, steaming is performed at 130°G for 30 minutes to develop color. Washing with water followed by hot water to desize and reduction washing yields a strong yellow print.

Example 48゜Stannous chloride 10 parts - Sannol 7000 (aromatic carrier) 10 parts Locust bean gum 12% aqueous solution 60 parts Water 20 parts Total 100 parts The above was mixed in a homomixer to prepare a discharge printing paste and carried out. Example 4
Print on the red dyed cloth described in 3. 130°G after intermediate drying
Steam for 20 minutes. Next, by washing with water, hot water, and reduction washing, a dyed cloth with a shiro pattern with excellent white discoloration of the discharge-printed paste stamped area can be obtained.

Example 49 Soda carbonate, Otoji glycerin 10 parts Sorbitose C-5 (etherified starch-based glue) 5 parts Snow Algin S S L (sodium alginate-based glue)
55 parts Water 30 parts Total 100 parts The alkaline discharge printing paste having the above composition was printed on a processed polyester yarn fabric, and it was intermediately dried. Next, a printing dyeing paste having the following composition is overprinted.

Dye composition from the monoazo compound described in Example 2 6 parts Sorbitose C - 55 parts Snow Algin S 8 L 60 parts Water 34 parts Total 100 steps After intermediate drying, steaming at 130°C for 20 minutes, washing with water, washing with hot water, Reduce and wash. A red printed pattern-dyed fabric with excellent white discoloration in the area printed with alkaline discharge printing paste is obtained.

Patent applicant: Nippon Kayaku Co., Ltd.

Claims (2)

[Claims] (1) Formula (I) [In formula (I), 几 represents an alkyl group having 1 to 4 carbon atoms,
X is hydrogen or bromine, and K is the formula (company). (IV) or M ■ 几8 C Formula (II) , (IJIN, In (IV) and M, 几 is hydrogen, chloro, methyl group, methoxy group, ethoxy group, acetylamino group, propionylamino group group, benzoylamino group, methylsulfonylamino group or ethylsulfonylamino group, 1t2 is hydrogen, chloro, methyl group, methoxy group or ethoxy group, 1-43.R4
is hydrogen, an alkyl group having 1 to 4 carbon atoms, an allyl group, a benzyl group, a cyanoethyl group, an alkoxyalkyl group having 3 to 4 carbon atoms, a hydroxyalkyl group having 2 to 4 carbon atoms, an acyloxyalkyl group having 4 to 6 carbon atoms , an alkoxycarbonylalkyl group having 3 to 7 carbon atoms or an alkoxycarbonyloxyalkyl group having 4 to 7 carbon atoms (however, R4 is not both hydrogen), It is chloro, methyl group, or ethyl group, R6 is hydrogen, methyl group or noenyl group, 几7 is methyl group or alkoxycarbonyl group having 2 to 5 carbon atoms '%', Rg is hydrogen, carbon number 1 to 4
each represents an alkyl group or an alkoxyalkyl group having 4 to 7 carbon atoms) (2) Formula (I) [In formula (I), R is an alkyl group having 1 to 4 carbon atoms,
X is hydrogen or bromine, and I is a formula. (IIJ), (IV) or M 8 (Formula (II), (III), QV) and M, R1 is hydrogen, chloro, methyl group, methoxy group, ethoxy group, acetylamino group, propionylamino group, benzoylamino group group, methylsulfonylamino group or ethylsulfonylamino group, (2 is hydrogen, chloro, methyl group, methoxy group or ethoxy group, group, cyanoethyl group, alkoxyalkyl group having 3 to 4 carbon atoms, hydroxyalkyl group having 2 to 4 carbon atoms, 4 to 4 carbon atoms
R5 is chloro , methyl group or ethyl group, JL is hydrogen, methyl group or phenyl group, L is methyl group or alkoxycarbonyl group having 2 to 5 carbon atoms, R8 is hydrogen, alkyl group having 1 to 4 carbon atoms, or carbon number A method for dyeing hydrophobic fibers characterized by using an insoluble monoazo compound represented by (representing each of 4 to 7 alkoxyalkyl groups)